THE EFFECT OF GRAPHENE NANOPLATELETS ON THE STRUCTURAL AND MECHANICAL PROPERTIES OF GLASS FIBER REINFORCED PA6 COMPOSITES

Öz

In this study, the mechanical, thermal, and microstructural properties of nanocomposites produced by adding graphene nanoplatelets (GnP) at different contents (1 wt%, 2 wt%, and 3 wt%) to commercially available polyamide 6 (PA6) and glass fiber (GF)–based composites were investigated. The composites were prepared via melt extrusion and subsequently injection molded to obtain test specimens. The produced samples were characterized through tensile, impact, hardness, density, moisture content, and melt flow index (MFI) tests, while their microstructure was examined using scanning electron microscopy (SEM). The findings show that the addition of GnP enhances stiffness by increasing the elastic modulus, whereas higher GnP contents limit impact strength and elongation at break. At 3 wt% GnP, the elastic modulus increased by 14%, while elongation at break and impact strength decreased by 14% and 19%, respectively. Furthermore, the addition of 1 wt% GnP resulted in a 145% increase in MFI, indicating a significant improvement in processability. Overall, the results present a comprehensive evaluation of the relationship between mechanical behavior, microstructure, and processability in glass fiber–reinforced PA6 composites containing GnP, demonstrating that even very low GnP contents can considerably influence composite performance. The originality of this study lies in quantitatively revealing the structure–property relationship induced by very low GnP contents in the glass fiber–reinforced PA6 matrix and in providing a detailed explanation of the conflicting effects between processability and mechanical performance.

Anahtar Kelimeler

• Polyamide 6
• Glass Fiber
• Graphene Nanoplatelets
• Polymer Composite
• Polymer Nanocomposite

GRAFEN NANOPLAKALARIN CAM ELYAF TAKVİYELİ PA6 KOMPOZİTLERİN YAPISAL VE MEKANİK ÖZELLİKLERİNE ETKİSİ

Öz

Bu çalışmada, poliamid 6 (PA6) ve cam elyaf (CE) esaslı hazır kompozitlere, farklı oranlarda (ağırlıkça %1, %2 ve %3) grafen nanoplakalar (GnP) eklenerek elde edilen nanokompozitlerin mekanik, termal ve mikroyapısal özellikleri incelenmiştir. Kompozitler, eriyik ekstrüzyon yöntemiyle hazırlanmış ve ardından enjeksiyon kalıplama ile test numuneleri üretilmiştir. Üretilen numuneler; çekme, darbe, sertlik, yoğunluk, nem oranı ve eriyik akış indeksi (MFI) gibi testlerle karakterize edilmiş, mikroyapı ise taramalı elektron mikroskobu (SEM) ile değerlendirilmiştir. Elde edilen bulgular, GnP ilavesinin elastisite modülünü artırarak rijitliği geliştirdiğini, ancak artan GnP oranının darbe dayanımı ve kopma uzamasını sınırladığını göstermektedir. %3 GnP içeriğinde elastisite modülü %14 artarken, kopma uzaması %14 ve darbe dayanımı %19 azalmıştır. Ayrıca %1 GnP katkısıyla MFI değerinde %145’lik artış elde edilmiş ve işlenebilirlikte belirgin bir iyileşme sağlanmıştır. Bu sonuçlar, GnP’nin cam elyaf takviyeli PA6 kompozitlerde mekanik davranış, mikroyapı ve işlenebilirlik arasındaki ilişkiyi inceleyen kapsamlı bir değerlendirme sunmakta; çok düşük GnP oranlarının dahi performansı önemli ölçüde etkileyebileceğini göstermektedir. Çalışmanın özgün katkısı, GnP’nin cam elyaf takviyeli PA6 matrisindeki çok düşük katkı oranlarında dahi oluşturduğu yapı–özellik ilişkisini nicel olarak ortaya koyması ve özellikle işlenebilirlik ile mekanik performans arasındaki çelişkili etkiyi detaylı şekilde açıklamasıdır.

Anahtar Kelimeler

• Poliamid 6
• Cam Elyaf
• Grafen Nanoplaka
• Polimer Kompozit
• Polimer Nanokompozit

Kaynakça

1. Akkapeddi, M. K., 2000. Glass Fiber Reinforced Polyamide‐6 Nanocomposites. Polymer Composites, 21(4), 576-585. https://doi.org/10.1002/pc.10213
2. Altay, L., Atagür, M., Erbektaş, M., Sarikanat, M., 2019. Grafit Nanoplaka Takviyeli Ultra Yüksek Molekül Ağırlıklı Polietilen Tabanlı Nano-Kompozit Malzeme Geliştirilmesi ve Karakterizasyonu Development and Characterization of Graphite Nanoplate Reinforced Ultra High Molecular Weight Polyethylene Based Nano-Composite Materials.
3. Aranha, R., Filho, M. A. A., De Lima Santos, C., Fonseca, V. M., Rivera, J. L. V., De Lima, A. G. B., De Amorim, W. F., Carvalho, L. H., 2023. Water Sorption in Hybrid Polyester/Glass/Jute Composites Processed via Compression Molding and Vacuum-Assisted Resin Transfer Molding. Polymers, 15(22), 4438. https://doi.org/10.3390/polym15224438
4. Botelho, E., 2003. Mechanical Behavior of Carbon Fiber Reinforced Polyamide Composites. Composites Science and Technology, 63(13), 1843-1855. https://doi.org/10.1016/S0266-3538(03)00119-2
5. Chaichanawong, J., Thongchuea, C., Areerat, S., 2016. Effect of Moisture On The Mechanical Properties of Glass Fiber Reinforced Polyamide Composites. Advanced Powder Technology, 27(3), 898-902. https://doi.org/10.1016/j.apt.2016.02.006
6. Chatterjee, S., Nüesch, F. A., Chu, B. T. T., 2013. Crystalline and tensile properties of carbon nanotube and graphene reinforced polyamide 12 fibers. Chemical Physics Letters, 557, 92-96. https://doi.org/10.1016/j.cplett.2012.11.091
7. Cui, Y., Kundalwal, S. I., Kumar, S., 2016. Gas Barrier Performance of Graphene/Polymer Nanocomposites. Carbon, 98, 313-333. https://doi.org/10.1016/j.carbon.2015.11.018
8. Çakir, M., Berberoğlu, B., 2018. E-Cam Elyaf Takviyeli Epoksi Matrisli Kompozit Malzemelerin Elyaf Oranındaki Artış İle Mekanik Özelliklerindeki Değişimlerin İncelenmesi. El-Cezeri Fen ve Mühendislik Dergisi, 5(3), 734-740. https://doi.org/10.31202/ecjse.415482

9. Dias, E., Chalse, H., Mutha, S., Mundhe, Y., Ambhore, N., Kulkarni, A., Mache, A., 2023. Review On Synthetic/Natural Fibers Polymer Composite Filled With Nanoclay and Their Mechanical Performance. Materials Today: Proceedings, 77, 916-925. https://doi.org/10.1016/j.matpr.2022.12.059
10. Ding, P., Su, S., Song, N., Tang, S., Liu, Y., Shi, L., 2014. Highly Thermal Conductive Composites With Polyamide-6 Covalently-Grafted Graphene By An İn Situ Polymerization and Thermal Reduction Process. Carbon, 66, 576-584. https://doi.org/10.1016/j.carbon.2013.09.041
11. Ferreño, D., Carrascal, I., Ruiz, E., Casado, J. A., 2011. Characterisation By Means of A Finite Element Model of The İnfluence of Moisture Content On The Mechanical and Fracture Properties of The Polyamide 6 Reinforced With Short Glass Fibre. Polymer Testing, 30(4), 420-428. https://doi.org/10.1016/j.polymertesting.2011.03.001
12. Fu, X., Yao, C., Yang, G., 2015. Recent Advances İn Graphene/Polyamide 6 Composites: A Review. RSC Advances, 5(76), 61688-61702. https://doi.org/10.1039/C5RA09312K
13. Gomez, J., Villaro, E., Karagiannidis, P. G., Elmarakbi, A., 2020. Effects of Chemical Structure and Morphology of Graphene-Related Materials (Grms) On Melt Processing and Properties of GRM/Polyamide-6 Nanocomposites. Results in Materials, 7, 100105. https://doi.org/10.1016/j.rinma.2020.100105
14. Gong, Y., Yang, G., 2009. Manufacturing and Physical Properties of All-Polyamide Composites. Journal of Materials Science, 44(17), 4639-4644. https://doi.org/10.1007/s10853-009-3708-0
15. Güllü, A., Özdemir, A., Özdemir, E., 2006. Experimental İnvestigation of The Effect Of Glass Fibres On The Mechanical Properties of Polypropylene (PP) and Polyamide 6 (PA6) Plastics. Materials & Design, 27(4), 316-323. https://doi.org/10.1016/j.matdes.2004.10.013
16. Hsissou, R., Abbout, S., Berisha, A., Berradi, M., Assouag, M., Hajjaji, N., Elharfi, A., 2019. Experimental, DFT and Molecular Dynamics Simulation On The İnhibition Performance of The DGDCBA Epoxy Polymer Against The Corrosion of The E24 Carbon Steel İn 1.0 M Hcl Solution. Journal of Molecular Structure, 1182, 340-351. https://doi.org/10.1016/j.molstruc.2018.12.030
17. Hsissou, R., Seghiri, R., Benzekri, Z., Hilali, M., Rafik, M., Elharfi, A., 2021b. Polymer Composite Materials: A Comprehensive Review. Composite Structures, 262, 113640. https://doi.org/10.1016/j.compstruct.2021.113640
18. Hu, K., Kulkarni, D. D., Choi, I., Tsukruk, V. V., 2014. Graphene-Polymer Nanocomposites For Structural and Functional Applications. Progress in Polymer Science, 39(11), 1934-1972. https://doi.org/10.1016/j.progpolymsci.2014.03.001
19. Kausar, A., 2018. Composite Coatings of Polyamide/Graphene: Microstructure, Mechanical, Thermal, and Barrier Properties. Composite Interfaces, 25(2), 109-125. https://doi.org/10.1080/09276440.2017.1340020
20. Kausar, A., Anwar, Z., Muhammad, B., 2017. Overview of Nonflammability Characteristics of Graphene and Graphene Oxide-Based Polymeric Composite and Essential Flame Retardancy Techniques. Polymer-Plastics Technology and Engineering, 56(5), 488-505. https://doi.org/10.1080/03602559.2016.1233274
21. Khademinejad, S., Mehdipour-Ataei, S., 2017. Aromatic Polyamide/Sepiolite Nanocomposite Materials: Synthesis, Structure, and Properties. Polymer-Plastics Technology and Engineering, 56(17), 1916-1922. https://doi.org/10.1080/03602559.2017.1295315
22. Kong, N., Khalil, N. Z., Fricke, H., 2021. Moisture Absorption Behavior and Adhesion Properties of GNP/Epoxy Nanocomposite Adhesives. Polymers, 13(11), 1850. https://doi.org/10.3390/polym13111850
23. Lee, P.-C., Kim, S. Y., Ko, Y. K., Ha, J. U., Jeoung, S. K., Shin, D., Kim, J. H., Kim, M.-G., 2022. Tribological Properties of Polyamide 46/Graphene Nanocomposites. Polymers, 14(6), 1139. https://doi.org/10.3390/polym14061139
24. Lee, S. J., Yoon, S. J., Jeon, I.-Y., 2022. Graphene/Polymer Nanocomposites: Preparation, Mechanical Properties, and Application. Polymers, 14(21), 4733. https://doi.org/10.3390/polym14214733
25. Li, H., Xu, Y., Zhang, T., Niu, K., Wang, Y., Zhao, Y., Zhang, B., 2020. Interfacial Adhesion and Shear Behaviors of Aramid Fiber/Polyamide 6 Composites Under Different Thermal Treatments. Polymer Testing, 81, 106209. https://doi.org/10.1016/j.polymertesting.2019.106209
26. Li, Q., Li, B., Zhang, S., Lin, M., 2012. Investigation On Effects of Aluminum and Magnesium Hypophosphites On Flame Retardancy and Thermal Degradation of Polyamide 6. Journal of Applied Polymer Science, 125(3), 1782-1789. https://doi.org/10.1002/app.35678
27. Liang, J., 2019. Impact Fracture Behavior and Morphology of Polypropylene/Graphene Nanoplatelets Composites. Polymer Composites, 40(S1). https://doi.org/10.1002/pc.24826
28. Lin, G., Xie, G., Sui, G., Yang, R., 2012. Hybrid Effect of Nanoparticles With Carbon Fibers On The Mechanical and Wear Properties of Polymer Composites. Composites Part B: Engineering, 43(1), 44-49. https://doi.org/10.1016/j.compositesb.2011.04.029
29. Madhad, H. V., Vasava, D. V., 2022. Review On Recent Progress İn Synthesis of Graphene–Polyamide Nanocomposites. Journal of Thermoplastic Composite Materials, 35(4), 570-598. https://doi.org/10.1177/0892705719880942
30. Mohan, V. B., Lau, K., Hui, D., Bhattacharyya, D., 2018. Graphene-Based Materials and Their Composites: A Review On Production, Applications and Product Limitations. Composites Part B: Engineering, 142, 200-220. https://doi.org/10.1016/j.compositesb.2018.01.013
31. O’Neill, A., Bakirtzis, D., Dixon, D., 2014. Polyamide 6/Graphene Composites: The Effect of İn Situ Polymerisation On The Structure and Properties of Graphene Oxide and Reduced Graphene Oxide. European Polymer Journal, 59, 353-362. https://doi.org/10.1016/j.eurpolymj.2014.07.038
32. Pan, Y., Hong, N., Zhan, J., Wang, B., Song, L., Hu, Y., 2014. Effect of Graphene on the Fire and Mechanical Performances of Glass Fiber-Reinforced Polyamide 6 Composites Containing Aluminum Hypophosphite. Polymer-Plastics Technology and Engineering, 53(14), 1467-1475. https://doi.org/10.1080/03602559.2014.909483
33. Prolongo, S. G., Jiménez-Suárez, A., Moriche, R., Ureña, A., 2018. Influence of Thickness and Lateral Size of Graphene Nanoplatelets on Water Uptake in Epoxy/Graphene Nanocomposites. Applied Sciences, 8(9), 1550. https://doi.org/10.3390/app8091550
34. Quan, H., Zhang, B., Zhao, Q., Yuen, R. K. K., Li, R. K. Y., 2009. Facile Preparation and Thermal Degradation Studies of Graphite Nanoplatelets (Gnps) Filled Thermoplastic Polyurethane (TPU) Nanocomposites. Composites Part A: Applied Science and Manufacturing, 40(9), 1506-1513. https://doi.org/10.1016/j.compositesa.2009.06.012
35. Ramanathan, T., Abdala, A. A., Stankovich, S., Dikin, D. A., Herrera-Alonso, M., Piner, R. D., Adamson, D. H., Schniepp, H. C., Chen, X., Ruoff, R. S., Nguyen, S. T., Aksay, I. A., Prud’Homme, R. K., Brinson, L. C., 2008. Functionalized Graphene Sheets For Polymer Nanocomposites. Nature Nanotechnology, 3(6), 327-331. https://doi.org/10.1038/nnano.2008.96
36. Rashmi, B. J., Prashantha, K., Lacrampe, M. ‐F., Krawczak, P., 2018. Scalable Production of Multifunctional Bio‐Based Polyamide 11/Graphene Nanocomposites by Melt Extrusion Processes Via Masterbatch Approach. Advances in Polymer Technology, 37(4), 1067-1075. https://doi.org/10.1002/adv.21757
37. Sathishkumar, T., Satheeshkumar, S., Naveen, J., 2014. Glass Fiber-Reinforced Polymer Composites – A Review. Journal of Reinforced Plastics and Composites, 33(13), 1258-1275. https://doi.org/10.1177/0731684414530790
38. Shen, M.-Y., Chang, T.-Y., Hsieh, T.-H., Li, Y.-L., Chiang, C.-L., Yang, H., Yip, M.-C., 2013. Mechanical Properties and Tensile Fatigue of Graphene Nanoplatelets Reinforced Polymer Nanocomposites. Journal of Nanomaterials, 2013(1), 565401. https://doi.org/10.1155/2013/565401
39. Song, P., Cao, Z., Cai, Y., Zhao, L., Fang, Z., Fu, S., 2011. Fabrication of Exfoliated Graphene-Based Polypropylene Nanocomposites With Enhanced Mechanical and Thermal Properties. Polymer, 52(18), 4001-4010. https://doi.org/10.1016/j.polymer.2011.06.045
40. Song, X., Wang, Y., Jiao, C., Huang, M., Wang, G.-H., Jiang, H., 2020. Microstructure Regulation of Polyamide Nanocomposite Membrane By Functional Mesoporous Polymer For High-Efficiency Desalination. Journal of Membrane Science, 597, 117783. https://doi.org/10.1016/j.memsci.2019.117783
41. Tarhini, A. A., Tehrani-Bagha, A. R., 2019. Graphene-Based Polymer Composite Films With Enhanced Mechanical Properties and Ultra-High İn-Plane Thermal Conductivity. Composites Science and Technology, 184, 107797. https://doi.org/10.1016/j.compscitech.2019.107797
42. Ulutas, E., Tasdemir, M., 2024. Engineering The Microstructure: Unveiling The Synergistic Effects of Gnp and Blowing Agents On PA6 Composite Foams. Materials Today Communications, 41, 110995. https://doi.org/10.1016/j.mtcomm.2024.110995
43. Ulutaş, E., Taşdemir, M., Korkmaz, Ö. F., Kuvvet, N., Duran, M. C., 2024. Polipropilen/Montmorillonit Kompozit Köpüğünün Fiziksel, Termal Ve Morfolojik Özelliklerinin İncelenmesi. Gümüşhane Üniversitesi Fen Bilimleri Enstitüsü Dergisi. https://doi.org/10.17714/gumusfenbil.1444336
44. Vaggar, G. B., Kamate, S. C., 2020. Thermal Property Characterization For Enhancement of Thermal Conductivity Of Hybrid Polymer Composites. Materials Today: Proceedings, 20, 208-212. https://doi.org/10.1016/j.matpr.2019.11.055
45. Vallés, C., Papageorgiou, D. G., Lin, F., Li, Z., Spencer, B. F., Young, R. J., Kinloch, I. A., 2020. PMMA-Grafted Graphene Nanoplatelets To Reinforce The Mechanical and Thermal Properties of PMMA Composites. Carbon, 157, 750-760. https://doi.org/10.1016/j.carbon.2019.10.075
46. Van De Werken, N., Tekinalp, H., Khanbolouki, P., Ozcan, S., Williams, A., Tehrani, M., 2020. Additively Manufactured Carbon Fiber-Reinforced Composites: State of The Art and Perspective. Additive Manufacturing, 31, 100962. https://doi.org/10.1016/j.addma.2019.100962
47. Vasiljević, J., Demšar, A., Leskovšek, M., Simončič, B., Čelan Korošin, N., Jerman, I., Šobak, M., Žitko, G., Van De Velde, N., Čolović, M., 2020. Characterization of Polyamide 6/Multilayer Graphene Nanoplatelet Composite Textile Filaments Obtained Via In Situ Polymerization and Melt Spinning. Polymers, 12(8), 1787. https://doi.org/10.3390/polym12081787
48. Von Turkovich, R., Erwin, L., 1983. Fiber Fracture İn Reinforced Thermoplastic Processing. Polymer Engineering &Science, 23(13), 743-749. https://doi.org/10.1002/pen.760231309
49. Wang, W., Ma, X., Sun, D., Qi, X., Yang, J., Wang, Y., 2020. Achieving Electrical İnsulation, High Thermal Conductivity and High Fracture Toughness İn Polyamide 6/Carbon Nanofiber Composites Through The İnterfacial Welding Effect of Elastomer. Composites Part A: Applied Science and Manufacturing, 128, 105671. https://doi.org/10.1016/j.compositesa.2019.105671
50. Yang, S.-Y., Lin, W.-N., Huang, Y.-L., Tien, H.-W., Wang, J.-Y., Ma, C.-C. M., Li, S.-M., Wang, Y.-S., 2011. Synergetic Effects of Graphene Platelets and Carbon Nanotubes On The Mechanical and Thermal Properties of Epoxy Composites. Carbon, 49(3), 793-803. https://doi.org/10.1016/j.carbon.2010.10.014
51. Zeng, H., Gao, C., Wang, Y., Watts, P. C. P., Kong, H., Cui, X., Yan, D., 2006. In Situ Polymerization Approach To Multiwalled Carbon Nanotubes-Reinforced Nylon 1010 Composites: Mechanical Properties and Crystallization Behavior. Polymer, 47(1), 113-122. https://doi.org/10.1016/j.polymer.2005.11.009
52. Zhang, X., Fan, X., Li, H., Yan, C., 2012. Facile Preparation Route For Graphene Oxide Reinforced Polyamide 6 Composites Via İn Situ Anionic Ring-Opening Polymerization. Journal of Materials Chemistry, 22(45), 24081. https://doi.org/10.1039/c2jm34243j
53. Żurawik, R., Volke, J., Zarges, J.-C., Heim, H.-P., 2021. Comparison of Real and Simulated Fiber Orientations in Injection Molded Short Glass Fiber Reinforced Polyamide by X-ray Microtomography. Polymers, 14(1), 29. https://doi.org/10.3390/polym14010029